Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM II-O-1.4 PREPARATION OF HYBRID TRANSPARENT ELECTRODES OF SILVER NANOWIRES AND CHEMICALLY CONVERTED GRAPHENE ON ABITRARY SUBSTRATE AT LOW TEMPERATURE Hoang Thi Thu, Huynh Tran My Hoa, Tran Quang Trung Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM E-mail: htthu@hcmus.edu.vn ABSTRACT Graphene has enjoyed significant recent attention due to its potential applications in electronic and optoelectronic devices Graphene is usually prepared via Hummers' method or modified Hummers' methods These method are the most suitable for the large-scale production of single graphene at low cost but the main drawbacks of these method are the use of strong oxidizing agents make graphene films were separated small sheets leading to extremely decrease its electrical conductivity Herein, we report an inexpensive, fast and facile method for preparation of a double layer structured transparent, flexible hybrid electrode from silver nanowires (Ag NWs) with chemically converted graphene (CCG) coating on arbitrary substrate These films dramatically decreases the resistance of graphene films and exhibited high optical transmittance (82.4%) and low sheet resistance (18 Ω/□), which is comparable to ITO transparent electrode They also show the ratio of direct conductivity to optical conductivity DC/OP = 104 is very close to that displayed by commercially available ITO Especially, the whole fabrication process is carried out at low temperature The graphene films is spin coating directly on the substrate without transferring, eliminated many troubles bring back from transfer method Key words: graphene, silver nanowires, conducting films, hybrid electrodes, low temperature INTRODUCTION Transparent and conducting metal oxides such as indium tin oxide (ITO) have been widely used as an essential element of various optoelectronic devices such as organic light-emitting diode (OLED) panels, touch screen panels, e-paper, and solar cells Vacuum deposited ITO transparent electrode possesses good physical properties such as high optical transmittance and low sheet resistance as a transparent electrode for various optoelectronic devices [1] However, it has several drawbacks such as brittleness and high processing temperature Furthermore, the scarcity of indium resources makes ITO transparent electrode very expensive recently Therefore, cheap, flexible, and solution-process able transparent electrodes have been required for next generation of optoelectronic devices such as flexible solar cells and displays Recently, new transparent electrode materials such as graphene, carbon nanotubes (CNT), and Ag nanowire (Ag NWs) films have been developed to replace conventional ITO transparent electrode [4-6,11,12] Among various ITO alternatives, Ag NWs films already showed the good optical and electrical performance comparable to ITO [9,13,14] Ag NWs are prepared by polyol method, which extremely low cost and facile Additional, Ag NWs films can be fabricated by many methods such as spin coating, bar coatings or spray coating but one of the drawbacks of Ag NWs films is that it can be easily oxidized when exposing to ambient condition for a long time Therefore, thermal oxidation stability of the Ag NWs films is much poorer than the competing transparent conductors such as CNT and graphene with theoretical values of charge carrier mobility higher than 200 000 cm2/V and single layer graphene only absorbs about 2.3% of visible light Although the CVD grown graphene have been used in various application areas, we should address some obstacles, such as catalyst material, growth conditions, etching problems, transfer technical and the high cost of CVD grapehene Fortunately, CCG is usually prepared by using chemical method that is the most suitable for the large-scale production of single graphene at low cost However, the main drawbacks of these method are the use of strong oxidizing agents make graphene sheets were small pieces (as show in fig 1a) leading to extremely decrease electrical conductivity of graphene films Fig 1c also show many defects in CCG films via Raman spectroscopy The Raman D band (~1365 cm−1) of graphene is activated by the defects that cause an intervalley double resonance involving transitions near two inequivalent K points at neighboring corners of the first Brillouin zone of graphene [7] To improve the conductive properties of chemical graphene films the authors have attempted to percolate more and more layers of rGO on the substrates (as shown in fig 1b) But this way is not efficiency in decrease resistance of the electrode (R = 21 000 Ω/sq with T = 78.13% at 550nm) The resistance too high to be applied to TCF for photovoltaic, which require sheet resistances of 10 Ω/sq to 50 Ω/sq approximately Just recently, Iskandar N.Kholmanov et al reported that they had experimentally verified this model by covering Ag NWs with single layer of graphene on glass substrate, and the obtained hybrid film exhibited the lowest sheet resistance of 64 Ω/sq (T = 93.6%) Following, Yang Liu et al had also ISBN: 978-604-82-1375-6 Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM successfully fabricated this model on flexible substrate with lowest sheet resistance of 32.5 Ω/sq (T = 81.5%) [15] Although hybrid transparent electrodes of Ag NWs and graphene are demonstrated in many publishes, only few additional attempts toward hybrid with chemical graphene are reported a ) b ) c) Figure Characterization of chemical graphene (a) AFM images of graphene oxide sheets with their height profiles (b) SEM image of many sheets of graphene (c) Raman spectroscopy of chemical graphene (1300−1400 cm) centered on the D mode (1365 cm) Therefore, in this work we demonstrate here experimentally the assembly of CCG with 1D Ag NWs The benefits of using this hybrid films are not only to connect the rGO islands but also to protect the fiber Ag from oxidation [6,8] CCG/Ag NWs hybrid films with TCF characteristics can comparable to that of ITO films (typically, Rs = 18 Ω/sq for an optical transmittance at λ = 550 nm T550 = 82.4%) The authors have fabricated transparent electrodes at a low temperature by adding Ag NWs to CCG The hybrid transparent electrodes on plastic films exhibited low sheet resistance, high transparency, and excellent flexibility These studies on hybrid transparent electrodes demonstrate the potential for the fabrication of electrical devices on plastic films by continuous roll-to-roll processes using a simple, inexpensive, and scalable process The goal of this study was to fabricate graphene hybrid films with a Ag NWs network on arbitrary substrate The process sequence of synthesizing CCG/Ag NWs hybrid films is illustrated in Fig Ag NWs dispersion in de-ionized water is spraying on a precleaned polyethylene terephthalate (PET) or glass substrate, followed by a spraying process, to form conductive subpercolating network of Ag NWs Then, several layer graphene films are spin coating on the top of the network of Ag NWs to form the final hybrid transparent electrodes, See experiment section for detailed information EXPERIMENT SECTION Synthesis of Ag NWs , GO The Ag NWs material was synthesized by polyol method and GO material was prepared by modified Hummer method at our laboratory More details were presented in our previous studies [2, 3] Optical transparency at the wavelength of 550 nm was measured using a UVVis spectrophotometer (JASCO Corp., Tokyo, Japan) with a glass or PET substrate as a reference The morphology of the samples were observed using a scanning electron microscope (SEM) (JSM-6700F, JEOL Ltd., Tokyo, Japan) and Atomic force microscope (AFM) (University of Ulsan, Daehak-ro 102, Nam-gu, Ulsan 680-749, South Korea) The sheet resistances of the hybrid films (before and after bending test) were measured using the four-probe method Fabrication of hybrid CCG/Ag NWs electrode The Ag NWs/CCG hybrid transparent electrode reported herein was fabricated on a glass or PET substrate with two steps Firstly, Ag NWS is spray coating on the arbitrary substrate to form Ag NWS network Then, GO solution is directly sequential spin coating on the Ag NWs network Finally, this hybrid films are exposure to hydrazine and heated to 150oC in the air condition to reduce to CCG films In this report, we fabricated Ag NWS networks on the arbitrary substrates with the same concentration of Ag NWs and conditional produce Through changing the thickness of CCG on the substrate, five samples were obtained and labeled with: H1, H2, H3, H4 and H5 We also prepared samples (only with CCG) with the same thickness corresponding with the thickness of CCG in the samples of hybrid to reference ISBN: 978-604-82-1375-6 10 Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM Figure Fabrication of graphene/Ag NW films Schematic illustration of hybrid film fabrication RESULTS AND DISCUSSION The morphology and structure of the as-synthesized Ag NWs was determined by SEM image (fig.3a) The Ag NWs is separated, majority, with 40-50 nm diameter and upper 20 µm length, and the rest amount of nanoparticles is insignificant [2] In this proceeding, the improvement of good contact among AgNWs network is extremely important and the annealing temperature is the key for solving this problem The heat treatment is not only removing the remained PVP on the surface of the AgNWs but also fuses the AgNWs together such that tight connections leading to high conductivity Figure shown the SEM image of the Ag NWs-CCG hybrid electrode, confirming that the Ag NWs create conductive bridges between graphene sheets leading to efficient in collecting and transporting the carriers to the external circuits Figure (a) SEM image of AgNW network ISBN: 978-604-82-1375-6 Figure SEM image of CCG/Ag NWs on glass substrate demonstrate that the Ag NWs bridge line defects and line disruptions (scale 500 nm) 11 Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM So these hybrid films show resistance 18 Ω/sq with T = 82.4% at 550nm (for glass substrate), while previously resistance of Ag NWS and Graphene is 75 Ω/sq and 350 000 Ω/sq repectively This means improved the electrical conductivity of the graphene films up to 2000 times To explain the vast improvement in sheet resistance of a Ag NWs-CCG electrode, we also agree with the explanation of Vincent at all that the formation of an extended conjugated network with individual Ag NWs bridging the gaps between graphene sheets The large graphene sheets cover the majority of the total surface area, while the Ag NWs act as wires connecting the large pads together [11] Figure Sheet resistance vs transmittance of Ag NWs, CCG and hybrid CCG/Ag NWs electrode Figure Transmittance of the AgNWs, CCG and the hybrid CCG/Ag NWs electrode without including the substrate In Fig and Fig 6, the optoelectronic performances of the CCG/Ag NWs films and CCG films are further compared From Fig 5, the transmittance of CCG/Ag NWs films are slightly reduced by 6% ~9%, which is due to the added layer of Ag NWs In contrast, from Fig 5, the sheet resistance of the obtained hybrid films are simultaneously reduced, which is even lower than that of Ag NWs film Therefore, another advantage of the coated Ag NWs can be concluded that it may play a role of increasing the conductivity of Graphene film through its unique electronic properties Recently, to evaluate optical and electrical properties of the thin films, the concept of aspect ratio DC/Op often used The higher the aspect ratio is the better the properties of TCO thin film The transmittance and sheet resistance for thin films are related by (1) expression, where Op is the optical conductivity (here quoted at 550 nm) and DC is the DC conductivity of the film [9,10] ISBN: 978-604-82-1375-6 12 Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM Table 1: The optical and electrical properties of hybrid silver nanowires/graphene film with respect to different molar ratio of rGO and Ag NWs Samples Resistance Ω/sq Transmittance % DC/OP Ag 75 90 46 Graphene 350 000 89 0.009 Hybrid 18 82.4 104 Graphene 150 000 87 0.017 Hybrid 17.5 81 97 Graphene 55 000 84 0.038 Hybrid 16 76 80 Graphene 40 000 82.84 0.048 Hybrid 15 72.5 72 Graphene 21 000 78.13 0.069 Hybrid 14.5 71 69.6 Figure Comparsion of σDC/σOp between Ag NWs and graphene/Ag NWs electrode CONCLUSION In this work, we report an inexpensive, fast and facile method for fabricate a flexible hybrid electrode from silver nanowires (Ag NWs) with rGO coating on arbitrary substrate These films significantly decrease the resistance of the bare rGO films and exhibited high optical transmittance (82.4%) and low sheet resistance (18 Ω/sq-1 ) They also show the ratio of direct conductivity to optical conductivity DC/OP = 104 at 2:1 molar ratio and 170oC annealing temperature is very close to that displayed TCO by commercially available ITO Especially, the whole fabrication process is carried out at low temperature The graphene films is spin coating directly on the substrate without transferring, eliminated many troubles bring back from transfer method ISBN: 978-604-82-1375-6 13 Báo cáo toàn văn Kỷ yếu hội nghị khoa học lần IX Trường Đại học Khoa học Tự nhiên, ĐHQG-HCM CHẾ TẠO ĐIỆN CỰC DẪN ĐIỆN TRONG SUỐT DỰA TRÊN TỔ HỢP LAI BẠC NANOWIRE VÀ GRAPHENE Ở NHIỆT ĐỘ THẤP Hoàng Thị Thu, Huỳnh Trần Mỹ Hòa, Trần Quang Trung Khoa Vật lý - Vật lý Kỹ thuật, Trường ĐH KHTN, ĐHQG-HCM TÓM TẮT Gần đây, Graphene ý ứng dụng tiềm thiết bị điện tử quang điện tử Graphene thường chế tạo phương pháp Hummer Hummer' cải tiến Các phương pháp thích hợp cho việc sản xuất quy mô lớn với chi phí thấp nhược điểm phương pháp việc sử dụng tác nhân oxy hóa mạnh làm cho màng graphene bị nát dẫn đến giảm đáng kể tính dẫn điện màng Trong báo này, trình bày phương pháp rẻ tiền, nhanh chóng đơn giản để chế tạo điện cực lai dựa dây nano bạc (Ag NWS) với graphene (CCG) đế tùy ý Những điện cực có điện trở thấp (18 Ω/□) độ truyền qua cao (82,4%), so sánh với điện cực suốt ITO Điện cực chế tạo có tỉ số DC/OP = 104 gần với đế ITO thương mại Đặc biệt, toàn trình chế tạo thực nhiệt độ thấp Các màng graphene quay phủ trực tiếp bề mặt đế mà không cần transfer, tránh nhiều khó khăn, hệ lụy phương pháp mang lại TÀI LIỆU THAM KHẢO [1] C.H Chung, T.B Song, B Bob, R Zhu, Y Yang Solution-Processed Flexible Transparent Conductors Composed of Silver Nanowire Networks Embedded in Indium Tin Oxide Nanoparticle Matrices, Springer Nano Res (2012) ISSN 1998-0124 [2] H T Thu, T Q Trung Preparation of silver nanowires by polyol method and their application for transparent conducting electrode, Sci Tech 50/1B (2012) 472-480 [3] Tran Quang Trung, Le Thi Lua, Tran Van Tam, Nguyen Thi Phuong Thanh, Huynh Tri Phong, Huynh Tran My Hoa The effect of annealing 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grapheme oxide/silvernano wire hybrids with high flexibility, Synthetic Metals 162 (15–16) (2012) 1364–1368 [9] S De, T M Higgins, P E Lyons, E M Doherty, P N Nirmalraj, W Blau, J J Boland, J N Coleman Silver Nanowire Networks as Flexible, Transparent, Conducting Films: Extremely High DC to Optical Conductivity Ratios, ACS Nano (7) (2009)1767–1774 [10] Dressel, M.; Gruner, G Electrodynamics of Solids: Optical Properties of Electrons in Matter; Cambridge University Cambridge, 2002 [11] V C Tung, L-M Chen, M J Allen, J K Wassei Low-Temperature Solution Processing of GrapheneCarbon Nanotube Hybrid Materials for High-Performance Transparent conductors, Nano Lett (5) (2009), 1949–1955 [12] Li, X L.; Zhang, G Y.; Bai, X D.; Sun, X M.; Wang, X R.; Wang, E.; Dai, H J.Nat - Highly conducting graphene sheets and Langmuir–Blodgett films - Nanotechnol 3, 2008, 538 [13] Erik C Garnett, Mark L Brongersma Self – Limited plasmonic welding of silve nanowire junctions Nature materials 11, (2012), 241–249 [14] Liqiang Yang, Tim Zhang, Wei you Solution – Processed Flexible Polymer Solar Cell with Silve Nanowire Electrodes ACS applied materials and interfaces 3, (2011), 4075-4084 [15] Yang Liu, Quanhong Chang and Lei Huang Transparent, flexible conducting graphene hybrid films with a subpercolating network of silver nanowires J Mater Chem C, 2013,1, 2970-2974 ISBN: 978-604-82-1375-6 14